JP7094107B2 - Surface-modified metal oxide particles, manufacturing method, dispersion, curable composition and cured product - Google Patents

Description

The present invention relates to surface-modified metal oxide particles and a method for producing the same, a dispersion containing surface-modified metal oxide particles and a curable composition, and a cured product obtained by curing the curable composition.

A cured product obtained by curing a curable composition can form a cured product having various shapes from the curable composition in a short time by (i) an imprint method, a casting method, or the like, and (ii) is less likely to break than glass. , (Iii) It is attracting attention as a material for an optical member instead of glass because it has advantages such as being lighter than glass. Conventionally, thermoplastic resins have been used for the same reason, but it has been pointed out that the yield due to spools and runners in the injection molding process is poor.

Optical members, especially lenses, may be required to reduce chromatic aberration. Therefore, as a curable composition, a cured product having a high Abbe number and high transparency may be required.

As a curable composition for an optical member, Patent Document 1 describes by reacting a first polymerizable component containing a fluorine-containing compound having a (meth) acryloyl group with a compound having a mercapto group and a carboxy group. A surface-modified metal oxide particle obtained by adding a mercapto group to a (meth) acryloyl group and surface-treated the surface of metal oxide particles (titania particles, zirconia particles, etc.) having a high refractive index; A photocurable composition comprising a second polymerizable component comprising a fluorine-containing compound having a (meth) acryloyl group; and a photopolymerization initiator has been proposed.

International Publication No. 2010/071134

However, on the surface of the surface-modified metal oxide particles in the curable composition proposed in Patent Document 1, a surface modifying group derived from a first polymerizable component other than the fluorine-containing compound, a mercapto group and a carboxy group are used. Since the proportion of the linking group derived from the compound has a large amount, it is difficult to increase the fluorine atom content in the surface modifying group.
Therefore, the surface-modified metal oxide particles in the curable composition of Patent Document 1 have poor compatibility with the fluorine-containing compound in the second polymerizable component. Therefore, in order to increase the Abbe number of the cured product, the proportion of the fluorine-containing compound in the second polymerizable component in the curable composition of Patent Document 1 may be increased, or the fluorine atom content of the fluorine-containing compound may be increased. Then, the surface-modified metal oxide particles cannot be uniformly dispersed in the second polymerizable component, and the transparency of the cured product is lowered.

The present invention is a surface-modified metal oxide particle having a fluoroalkyl group-containing surface modifying group and a (meth) acryloyl group-containing surface modifying group on the surface, and is easily dispersed in a liquid fluorine-containing compound having a high fluorine atom content. Surface-modified metal oxide particles and a method for producing the same; a dispersion liquid having a high Abbe number and excellent transparency; a curable composition capable of obtaining a cured product having a high Abbe number and excellent transparency; Provide a cured product having excellent properties.

The present invention has the following aspects.
<1> The first surface modifying group having a group represented by the following formula (A1) and the following formula (A2) on the surface of the metal oxide particles having a refractive index of 1.9 or more with respect to light having a wavelength of 589 nm. A surface-modified metal oxide particle having a second surface-modifying group having a group represented.
C _n F _m H _{2n + 1-m-} SiR ¹ _a (-*) _3-a (A1)
(* Is a bond of Si, R ¹ is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, n is an integer of 1 to 20, and m is an integer of 3 or more (2n + 1) or less. , A is an integer of 0 to 2, and when a is 2, the two ^R1s may be the same or different.)
CH ₂ = CR ³ C (O) -X- (CH ₂ ) _b -SiR ⁴ _c (-*) _3-c (A2)
(* Is a bond of Si, R ³ is a hydrogen atom or a methyl group, R ⁴ is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, and X is -O- or -NH-. , B is an integer of 2 to 10, c is an integer of 0 to 2, and when c is 2, the two ^R4s may be the same or different.)
<2> The ratio of the metal oxide particles to 100% by mass of the surface-modified metal oxide particles is 20 to 84% by mass, and the surface-modified organic component (the first surface-modifying group and the second surface-modifying group). The surface-modified metal oxide particles of <1>, wherein the (content) ratio of (total) is 16 to 80% by mass.
<3> Of 100% by mass of the surface-modified metal oxide particles, the ratio of the first surface-modifying group is 15 to 55% by mass, and the ratio of the second surface-modifying group is 1 to 25% by mass. 1> 1 or <2> surface-modified metal oxide particles.
<4> The surface of the metal oxide particles having a refractive index of 1.9 or more with respect to light having a wavelength of 589 nm is surface-treated by the compound represented by the following formula (A10) and the compound represented by the following formula (A20). A method for producing surface-modified metal oxide particles.
C _n F _m H _{2n + 1-m-} SiR ¹ _a (OR ² ) _3-a (A10)
(R ¹ , a, m and n are the same as the definitions in the formula (A1) of claim 1, respectively. R ² is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and a is 0. Or the three or ^two R2s in the case of 1 may be the same or different.)
CH ₂ = CR ³ C (O) -X- (CH ₂ ) _b -SiR ⁴ _c (OR ⁵ ) _3-c (A20)
(R ³ , R ⁴ , b and c are the same as the definitions in the formula (A2) of claim 1, respectively. R ⁵ is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and c is. The three or two ^R5s in the case of 0 or 1 may be the same or different.
<5> Of the total 100% by mass of the compound represented by the formula (A10) and the compound represented by the formula (A20), the compound represented by the formula (A10) is 39 to 98% by mass. The method for producing surface-modified metal oxide particles according to <4>, wherein the compound represented by the formula (A20) is 2 to 61% by mass.
<6> The total amount of the compound represented by the formula (A10) and the compound represented by the formula (A20) is 65 to 1360 parts by mass with respect to 100 parts by mass of the metal oxide particles, <4> or. <5> A method for producing surface-modified metal oxide particles.
<7> The surface-modified metal oxide particles of <1> to <3>; a fluorine-containing compound having a fluorine atom content of 20% by mass or more and being liquid at 25 ° C.; the surface-modified metal oxidation. A dispersion liquid in which the surface-modified metal oxide particles are 1 to 90% by mass and the fluorine-containing compound is 10 to 99% by mass in a total of 100% by mass of the physical particles and the fluorine-containing compound.
<8> The dispersion liquid of <7>, wherein the Abbe index obtained from the following formula (I) is 58 or more, and the transmittance of light having a wavelength of 600 nm is 40% or more.
ν _D = (n _D -1) / (n _F -n _C ) (I)
(Ν _D is the Abbe number, n _D is the index of refraction for light with a wavelength of 589 nm, n _F is the index of refraction for light with a wavelength of 486 nm, and n _C is the index of refraction for light with a wavelength of 656 nm. be.)
<9> With the surface-modified metal oxide particles (A) of <1> to <3>; the compound (B) having a fluorine atom content of 20% by mass or more and having one or more (meth) acryloyl groups. (However, the particles (A) are excluded.) And; a polymerization initiator (D) is included; the particles (A) and a compound having all (meth) acryloyl groups (however, the particles (A) are excluded). The particles (A) are 1 to 90% by mass and the compound (B) is 10 to 99% by mass out of a total of 100% by mass with the particles (A); the particles (A) and all (.). Meta) The curability of the polymerization initiator (D) is 0.01 to 10 parts by mass with respect to a total of 100 parts by mass with the compound having an acryloyl group (however, excluding the particles (A)). Composition.
<10> A compound (C) having one or more (meth) acryloyl groups (excluding the particles (A) and the compound (B)) is further included; the particles (A) and all (meth). Of the total 100% by mass of the compound having an acryloyl group (however, excluding the particle (A)), the particle (A) is 1 to 89% by mass, and the compound (B) is 10 to 10 to The curable composition of <9>, which is 98% by mass and the compound (C) is 1 to 50% by mass.
<11> A curable composition of <9> or <10>, wherein compound (B) is a fluoro (meth) acrylate.
<12> The compound (C) is a compound (C1) having one (meth) acryloyloxy group, or a compound (C2) having two or more (meth) acryloyloxy groups (provided that the compounds (C1) and (C2) are present. ) Is the same as the particles (A) or the compound (B)), the curable composition of <9> to <11>.
<13> A cured product obtained by curing the curable composition of <9> to <12>.

The surface-modified metal oxide particles of the present invention are likely to be dispersed in a liquid fluorine-containing compound having a high fluorine atom content. According to the method for producing surface-modified metal oxide particles of the present invention, surface-modified metal oxide particles that can be easily dispersed in a liquid fluorine-containing compound having a high fluorine atom content can be produced. The dispersion liquid of the present invention has a high Abbe number and is excellent in transparency. According to the curable composition of the present invention, a cured product having a high Abbe number and excellent transparency can be obtained.

In the present specification, the following terms are described with the following meanings, respectively.
The "compound represented by the formula (A10)" is also referred to as "compound (A10)". Compounds represented by other formulas are similarly described in the same manner.
"(Meta) acryloyl group" is a general term for acryloyl group and methacryloyl group.
"(Meta) acrylate" is a general term for acrylate and methacrylate.
"(Meta) acrylic acid" is a general term for acrylic acid and methacrylic acid.
"Light" is a general term for ultraviolet rays, visible rays, infrared rays, electron beams and radiation.

<Surface-modified metal oxide particles>
The surface-modified metal oxide particles of the present invention have a first surface modifying group described later and a second surface modifying group described later on the surface of the metal oxide particles. As the surface-modified metal oxide particles of the present invention, one type may be used alone, or two or more types having different metal oxide particles or surface-modifying groups may be used in combination.

The median diameter of the surface-modified metal oxide particles of the present invention is preferably 1 to 1000 nm, more preferably 1 to 100 nm. When the median diameter is at least the lower limit value, the handleability is good, and the primary particles are less likely to aggregate and are easily monodispersed. When the median diameter is not more than the upper limit, the transparency of the cured product is further excellent.

(Metal oxide particles)
The refractive index of the surface-unmodified metal oxide particles with respect to light having a wavelength of 589 nm is 1.9 or more, preferably 2.0 or more. When the refractive index is at least the lower limit of the above range, the Abbe number of the dispersion liquid and the cured product is high, and the refractive index is not significantly lowered. The higher the refractive index is, the better, but the refractive index of the existing oxide particles is usually 2.7 or less.

Examples of the metal oxide particles include zirconia particles, titania particles, zinc oxide particles, hafnium oxide, germanium oxide particles, niobium oxide particles, tantalum oxide particles, tungsten oxide particles, cerium oxide, indium oxide particles, tin oxide and the like. Of these, zirconia particles or titania particles, which have a high refractive index and good compatibility with other materials, are preferable.
The metal oxide particles may be solid particles, hollow particles, porous particles, or composite oxide particles.

The median diameter of the metal oxide particles before surface modification is preferably 1 to 1000 nm, more preferably 1 to 100 nm. When the median diameter is at least the lower limit value, the handleability is good, and the primary particles are less likely to aggregate and are easily monodispersed. When the median diameter is not more than the upper limit, the transparency of the cured product is further excellent.

(First surface modifying group)
The first surface modifying group is a surface modifying group having a group represented by the following formula (A1).
C _n F _m H _{2n + 1-m-} SiR ¹ _a (-*) _3-a (A1)

In the formula (A1), * is a Si bond. R ¹ is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. As the hydrocarbon group, an alkyl group is preferable, and a linear alkyl group is more preferable. As the alkyl group, a methyl group or an ethyl group is preferable from the viewpoint of handleability of the compound (A10) described later, and a methyl group is particularly preferable from the viewpoint of easy availability of the compound (A10).
n is an integer of 1 to 20, and an integer of 3 to 20 is preferable from the viewpoint of compatibility with a fluorine-containing compound having a high fluorine atom content, the effect on the environment is small, and the compound (A10) is obtained. From the viewpoint of ease of use, 3 to 10 is particularly preferable.
m is an integer of 3 or more (2n + 1) or less. When m is 3 or more, the compatibility with a fluorine-containing compound having a high fluorine atom content is improved. When n is an integer of 3 or more, m is preferably an integer of (2n-3) or less from the viewpoint of easy availability of the compound (A10).
a is an integer of 0 to 2, and an integer of 0 to 1 is preferable, and 0 is particularly preferable, from the viewpoint of the reactivity of the compound (A10). When a is 2, the two R ^1s may be the same or different.

Examples of the group represented by the formula (A1) include the following groups.
CF ₃ (CH ₂ ) ₂ Si (-*) ₃ , CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₂ Si (-*) ₃ ,
CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (-*) ₃ ,
CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (-*) ₃ etc.

(Second surface modifying group)
The second surface modifying group is a surface modifying group having a group represented by the following formula (A2).
CH ₂ = CR ³ C (O) -X- (CH ₂ ) _b -SiR ⁴ _c (-*) _3-c (A2)

In the formula (A2), * is a Si bond. R ³ is a hydrogen atom or a methyl group.
^R4 is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. As the hydrocarbon group, an alkyl group is preferable, and a linear alkyl group is more preferable. As the alkyl group, a methyl group or an ethyl group is preferable from the viewpoint of handleability of the compound (A20) described later, and a methyl group is particularly preferable from the viewpoint of easy availability of the compound (A20).
X is —O— or —NH—, and —O— is particularly preferred from the viewpoint of easy availability of compound (A20).
b is an integer of 2 to 10, preferably an integer of 2 to 8, more preferably an integer of 2 to 3, and particularly preferably 3 from the viewpoint of easy availability of the compound (A20). When the alkylene group in the second surface modifying group is a short chain having 10 or less carbon atoms (preferably 8 or less), a liquid fluorine-containing compound having a high fluorine atom content can approach the first surface modifying group. Therefore, the compatibility with the fluorine-containing compound of the liquid having a high fluorine atom content (specifically, 20% by mass or more) is further improved, and it is easy to disperse in the fluorine-containing compound.
c is an integer of 0 to 2, and an integer of 0 to 1 is preferable, and 0 is particularly preferable, from the viewpoint of the reactivity of the compound (A20). When c is 2, the two ^R4s may be the same or different.

Examples of the group represented by the formula (A2) include the following groups.
CH ₂ = C (CH ₃ ) C (O) O (CH ₂ ) ₃ Si (CH ₃ ) (-*) ₂ ,
CH ₂ = C (CH ₃ ) C (O) O (CH ₂ ) ₃ Si (-*) ₃ ,
CH ₂ = CHC (O) O (CH ₂ ) ₃ Si (-*) ₃ ,
CH ₂ = C (CH ₃ ) C (O) NH (CH ₂ ) ₃ Si (-*) ₃ ,
CH ₂ = CHC (O) NH (CH ₂ ) ₃ Si (-*) ₃ etc.

(Composition of surface-modified metal oxide particles)
The (content) ratio of the metal oxide particles is preferably 20 to 84% by mass, more preferably 30 to 75% by mass, out of 100% by mass of the surface-modified metal oxide particles. When the ratio is equal to or higher than the lower limit of the above range, the Abbe number is high and the refractive index is not significantly lowered. When the ratio is not more than the upper limit of the above range, the compatibility with the fluorine-containing compound is improved.

The ratio of the surface-modified organic component (total of the first surface-modifying group and the second surface-modifying group) is preferably 16 to 80% by mass, preferably 25 to 70% by mass, out of 100% by mass of the surface-modified metal oxide particles. % Is more preferable. When the ratio is at least the lower limit of the above range, the compatibility with the fluorine-containing compound is improved. When the ratio is not more than the upper limit of the above range, the Abbe number is high and the refractive index is not significantly lowered.

The ratio of the first surface modifying group is preferably 15 to 55% by mass, more preferably 20 to 50% by mass, out of 100% by mass of the surface-modified metal oxide particles. When the ratio is not more than the lower limit of the above range, the Abbe number of the cured product obtained by curing the curable composition containing the surface-modified metal oxide particles is sufficiently high. When the ratio is not more than the upper limit of the above range, the curable composition containing the surface-modified metal oxide particles is excellent in curability.

The ratio of the second surface modifying group is preferably 1 to 25% by mass, more preferably 5 to 20% by mass, out of 100% by mass of the surface-modified metal oxide particles. When the ratio is at least the lower limit of the above range, the curable composition containing the surface-modified metal oxide particles is excellent in curability. When the ratio is not more than the upper limit of the above range, the compatibility between the surface-modified metal oxide particles and the liquid fluorine-containing compound having a high fluorine atom content is excellent.

For the ratio of the metal oxide particles and the (content) ratio of the surface-modified organic component, the amount of thermal weight loss (that is, the amount of the surface-modified organic component) of the surface-modified metal oxide particles shall be measured using a thermal weight measuring device. Can be obtained by.
For the ratio of the first surface modifying group and the ratio of the second surface modifying group, the ratio of the group peculiar to each surface modifying group is obtained from the infrared spectroscopic spectrum, ¹⁹ F-NMR spectrum, etc. of the surface modified metal oxide particles. , Can be calculated from the ratio.

The surface-modified metal oxide particles of the present invention described above have metal oxide particles having a refractive index of 1.9 or more and have a first surface-modifying group having a fluoroalkyl group. A cured product having a high Abbe number can be obtained without significantly reducing the refractive index.
Further, since it has a first surface modifying group, the fluorine atom content in the surface modifying group can be increased, and it is easy to disperse in a liquid fluorine-containing compound having a high fluorine atom content.
Further, since it has a second surface modifying group, a cured product having excellent mechanical properties can be obtained by using it in combination with a compound having a (meth) acryloyl group and a polymerization initiator.

<Manufacturing method of surface-modified metal oxide particles>
The surface-modified metal oxide particles of the present invention can be obtained, for example, by surface-treating the surface of the metal oxide particles with the compound (A10) and the compound (A20).

Specifically, the compound (A10) and the compound (A20) are hydrolyzed in the presence of a catalyst by adding the compound (A10) and the compound (A20) to the dispersion liquid containing the metal oxide particles and water. , These hydrolysates are reacted with the hydroxyl groups on the surface of the metal oxide particles.

The surface of the metal oxide particles is surface-treated with the compound (A10) and the compound (A20) to obtain surface-modified metal oxide particles having a primary coating, and then the surface is further surface-treated with the compound (A10). Secondary coated surface-modified metal oxide particles may be obtained. The secondary coated particles are more excellent in compatibility with the fluorine-containing compound.

(Dispersion of metal oxide particles)
As the dispersion liquid of the metal oxide particles, a metal oxide sol (zirconia sol, titania sol, etc.) is used. The metal oxide particles may be used alone or in combination of two or more.
As the dispersion medium, water or a mixed solvent of water and a water-soluble organic solvent (alcohol or the like) is used. The concentration of the metal oxide particles is preferably 1 to 60% by mass, more preferably 5 to 40% by mass, still more preferably 10 to 20% by mass, out of 100% by mass of the dispersion liquid.

(Compound (A10))
The compound (A10) is a compound represented by the following formula.
C _n F _m H _{2n + 1-m-} SiR ¹ _a (OR ² ) _3-a (A10)

In formula (A10), R ¹ is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, R ² is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and n is an integer of 1 to 20. M is an integer of 3 or more (2n + 1) or less, a is an integer of 0 to 2, and when a is 2, the two ^R1s may be the same or different. The three or ^two R2s when a is 0 or 1 may be the same or different.
As the hydrocarbon group, an alkyl group is preferable, and a linear alkyl group is more preferable. As the alkyl group, a methyl group or an ethyl group is preferable from the viewpoint of the handleability and availability of the compound (A10). The three or ^two R2s when a is 0 or 1 may be the same or different.

Examples of the compound (A10) include trifluoropropyltrimethoxysilane, nonafluorohexyltrimethoxysilane, tridecafluorooctyltrimethoxysilane, heptadecafluorodecyltrimethoxysilane, trifluoropropyltriethoxysilane, and nonafluorohexyltriethoxysilane. , Tridecafluorooctyltriethoxysilane, heptadecafluorodecyltriethoxysilane and the like.
As the compound (A10), one kind may be used alone, or two or more kinds may be used in combination. When two or more kinds are used in combination, the compatibility with the fluorine-containing compound is improved as compared with the case where they are used alone.

The ratio of the compound (A10) is preferably 39 to 98% by mass, more preferably 52 to 92% by mass, out of a total of 100% by mass of the compound (A10) and the compound (A20). When the ratio is not more than the lower limit of the above range, the Abbe number of the cured product obtained by curing the curable composition containing the surface-modified metal oxide particles is sufficiently high. When the ratio is not more than the upper limit of the above range, the curable composition containing the surface-modified metal oxide particles is excellent in curability.
When the surface-modified metal oxide particles are secondarily coated, the ratio of the compound (A10) is the total ratio of the compounds (A10) used for the primary coating and the secondary coating.

(Compound (A20))
The compound (A20) is a compound represented by the following formula.
CH ₂ = CR ³ C (O) -X- (CH ₂ ) _b -SiR ⁴ _c (OR ⁵ ) _3-c (A20)

In formula (A20), R ³ is a hydrogen atom or a methyl group, R ⁴ is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, and R ⁵ is a hydrogen atom or a hydrocarbon having 1 to 10 carbon atoms. The group, X is -O- or -NH-, b is an integer of 2 to 10, c is an integer of 0 to 2, and when c is 2, the two ^R4s are the same. It may be present or different, and the three or two ^R5s when c is 0 or 1 may be the same or different.
As the hydrocarbon group, an alkyl group is preferable, and a linear alkyl group is more preferable. As the alkyl group, a methyl group or an ethyl group is preferable from the viewpoint of handleability and availability of the compound (A20). When c is 0 or 1, the three or two ^R5s may be the same or different.

Examples of the compound (A20) include 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloyloxypropyltri. Examples thereof include methoxysilane, 3- (isopropenylcarbonylamino) propyltrimethoxysilane, 3- (vinylcarbonylamino) propyltrimethoxysilane. As the compound (A20), one kind may be used alone, or two or more kinds may be used in combination.

The ratio of the compound (A20) is preferably 2 to 61% by mass, more preferably 8 to 48% by mass, based on 100% by mass of the total of the compound (A10) and the compound (A20). When the ratio is at least the lower limit of the above range, the curable composition containing the surface-modified metal oxide particles is excellent in curability. When the ratio is not more than the upper limit of the above range, the compatibility between the surface-modified metal oxide particles and the liquid fluorine-containing compound having a high fluorine atom content is excellent.

The total amount of the compound (A10) and the compound (A20) is preferably 65 to 1360 parts by mass, more preferably 113 to 793 parts by mass with respect to 100 parts by mass of the metal oxide particles. When the surface-modified metal oxide particles are secondarily coated, the amount of the compound (A10) is the total amount of the compound (A10) used for the primary coating and the secondary coating.

(catalyst)
Examples of the catalyst include acid catalysts, basic catalysts, ion exchange resins and the like. Examples of the acid catalyst include hydrochloric acid, nitric acid, acetic acid, sulfuric acid, phosphoric acid, sulfonic acid, methanesulfonic acid, p-toluenesulfonic acid and the like. Examples of the basic catalyst include sodium hydroxide, potassium hydroxide, ammonia, triethylamine and the like.

The temperature at the time of surface treatment is preferably 50 to 200 ° C, more preferably 80 to 150 ° C. When the dispersion medium is water, reflux is preferable. The surface treatment time may be appropriately determined depending on the temperature, concentration and the like, and is not particularly limited, but is preferably 1 to 24 hours, more preferably 3 to 12 hours.

<Dispersion of surface-modified metal oxide particles>
The dispersion liquid of the present invention comprises the surface-modified metal oxide particles of the present invention and a fluorine-containing compound having a fluorine atom content (hereinafter, also referred to as F content) of 20% by mass or more and being liquid at 25 ° C. including.

(Fluorine-containing compound)
The fluorine-containing compound, which is liquid at 25 ° C., functions as a dispersion medium for dispersing the surface-modified metal oxide particles of the present invention.

The F content of the fluorine-containing compound is 20% by mass or more, preferably 25 to 80% by mass, and more preferably 30 to 70% by mass. When the F content of the fluorine-containing compound is at least the lower limit of the above range, the Abbe number of the dispersion liquid of the present invention is sufficiently high. When the F content of the fluorine-containing compound is not more than the upper limit of the above range, the surface-modified metal oxide particles of the present invention are likely to be uniformly dispersed.

Examples of the fluorine-containing compound include a fluorine-containing organic solvent and the compound (B) described later.
Examples of the fluorine-containing organic solvent include hydrofluoroalkane, chlorofluorocarbon, hydrochlorofluorocarbon, hydrofluoromonoether, perfluoromonoether, perfluoroalkane, perfluoropolyether, perfluoroamine, fluorine atom-containing alken, and fluorine atom-containing aromatic solvent. Fluorine atom-containing ketones, fluorine atom-containing esters and the like can be mentioned. Commercially available products include, for example, Asahiclean (registered trademark of Asahi Glass Co., Ltd.) AK-225 (CF ₃ CF ₂ CHCl ₂ ), AC-2000 (CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CHF ₂ ), AC-6000 (CF). ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CH ₂ CH ₃ ), AE-3000 (CF ₃ CH ₂ OCF ₂ CHF ₂ ); Novec (trade name of Sumitomo 3M Corporation) 7100 (C ₄ F ₉ OCH ₃ ), 7200 (C ₄ F ₉ OC ₂ H ₅ ), 7300 (C ₂ F ₅ CF (OCH ₃ ) CF (CF ₃ ) ₂ ); Bertrel (trade name of Mitsui Dupont Fluorochemical Co., Ltd.) XF (CF ₃ CHFCHFC ₂ F ₅ ) , MCA, XH; Zeorora (trade name of Zeon Corporation, Japan) H (Heptafluorocyclopentane) and the like. Each of these compounds has an F content of 20% by mass or more.

The dispersion liquid of the present invention may contain an organic solvent or an additive other than the fluorine-containing compound, if necessary.
As the other organic solvent, those having no high polarity are preferable. Examples of other organic solvents include methyl ethyl ketone, methyl isobutyl ketone, toluene, hexane and the like.
Examples of the additive include a surfactant, an antioxidant, a thixotropic agent, an antifoaming agent, an antioxidant, a resin and the like.
Examples of the surfactant include Surflon (registered trademark of AGC Seimi Chemical Co., Ltd.) S-243, S-386, S-420, S-611, S-651, S-393, KH-20, etc .; Florard (Sumitomo 3M Ltd.). Product name) FC-170, FC-430, etc .; Megafuck (DIC company product name) F-552, F-553, F-554, F-556, etc. may be mentioned.
Examples of the antioxidant include IRGANOX (trade name of BASF Corporation) 1076, 1135, 1035, 1098, 1010, 1520L and the like. By adding an antioxidant, heat resistance is improved and yellowing is less likely to occur.

Examples of the thixotropic agent include DISPARLON (trade name of Kusumoto Kasei Co., Ltd.) 308, 301, 6500, 6700 and the like. By adding a thixotropic agent, the curable composition can be prevented from dripping or thickened when it is allowed to stand.
Examples of the defoaming agent include fluorosilicones (trimethyl-terminated trifluoropropylmethylsiloxane and the like), silicone oil and the like.

Examples of the antigelling agent include hydroquinone, hydroquinone monomethyl ether, 4-tert-butylcatechol, 3,5-dibutyl-4-hydroxytoluene, IRGASTAB (trade name of BASF) UV10, UV22 and the like. By adding the anti-gelling agent, it becomes easy to control the cured and uncured regions by the amount of light irradiated at the time of curing.
Examples of the resin include fluororesins and the like. By adding the resin, it is possible to suppress curing shrinkage, suppress thermal expansion, and impart mechanical strength.

(Ratio of each component of dispersion)
The (content) ratio of the surface-modified metal oxide particles is 1 to 90% by mass, preferably 3 to 85% by mass, and 5 to 85% by mass of the total 100% by mass of the surface-modified metal oxide particles and the fluorine-containing compound. 80% by mass is more preferable. When the ratio is equal to or higher than the lower limit of the above range, the Abbe number of the dispersion liquid becomes high. When the ratio is not more than the upper limit of the above range, the compatibility with other components is good, the surface-modified metal oxide particles are easily dispersed uniformly in the dispersion liquid, and the transparency of the dispersion liquid is excellent.

The proportion of the fluorine-containing compound is 10 to 99% by mass, preferably 15 to 97% by mass, and more preferably 20 to 95% by mass, out of a total of 100% by mass of the surface-modified metal oxide particles and the fluorine-containing compound. .. When the ratio is equal to or higher than the lower limit of the above range, the Abbe number of the dispersion liquid becomes sufficiently high. When the ratio is not more than the upper limit of the above range, the compatibility with other components is good and the transparency of the dispersion is excellent.

The amount of the other organic solvent added is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, based on 100 parts by mass of the total of the surface-modified metal oxide particles and the fluorine-containing compound. The total amount of other components added, such as additives, is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, based on 100 parts by mass of the total of the surface-modified metal oxide particles and the fluorine-containing compound.

The Abbe number obtained from the following formula (I) of the dispersion is preferably 58 or more, more preferably 60 or more. If the Abbe number is equal to or greater than the lower limit of the above range, chromatic aberration is unlikely to occur. The higher the Abbe number, the better, and the upper limit is not particularly limited, but it is about 70 considering that it is an organic substance.
ν _D = (n _D -1) / (n _F -n _C ) (I)
However, ν _D is an Abbe number, n _D is the refractive index for light having a wavelength of 589 nm, n _F is the refractive index for light having a wavelength of 486 nm, and n _C is the refractive index for light having a wavelength of 656 nm. Is.

The transmittance of the dispersion liquid having a wavelength of 600 nm is preferably 40% or more, more preferably 45% or more. When the light transmittance is at least the above lower limit value, the transparency is further excellent.
The transmittance of light having a wavelength of 600 nm in the dispersion is 25 using light having a wavelength of 600 nm by the method described in JIS K 7361: 1997 (ISO 13468-1: 1996) for the dispersion in a quartz cell having an optical path length of 10 mm. Measured at ° C.

(Manufacturing method of dispersion)
The dispersion liquid of the present invention is obtained by mixing the surface-modified metal oxide particles of the present invention with a fluorine-containing compound. The surface-modified metal oxide particles may be in the state of powder or in the state of a dispersion liquid dispersed in an organic solvent other than the fluorine-containing compound.

The dispersion liquid of the present invention described above contains surface-modified metal oxide particles having a first surface-modifying group on the surface and a fluorine-containing compound having an F content of 20% by mass or more. The number is high. Further, it has good compatibility with a liquid fluorine-containing compound having a high F content, and is excellent in transparency because it contains surface-modified metal oxide particles that are easily dispersed in the fluorine-containing compound.

<Curable composition>
The curable composition of the present invention comprises the surface-modified metal oxide particles of the present invention (hereinafter, also referred to as surface-modified metal oxide particles (A)), the compound (B), and the polymerization initiator (D). Included as an essential ingredient.

The viscosity of the curable composition of the present invention at 25 ° C. is preferably 10 to 15000 mPa · s, more preferably 100 to 12000 mPa · s. If the viscosity is within the above range, the curable composition can be easily molded into an imprint mold without performing a special operation (for example, an operation of heating the curable composition to a high temperature to reduce the viscosity). It can be contacted or easily injected into a mold for casting. Further, the curable composition can be easily applied to the surface of the base material without the curable composition flowing out from the surface of the base material.

(Compound (B))
The compound (B) has an F content of 20% by mass or more and has one or more (meth) acryloyl groups.
The F content of the compound (B) is 20% by mass or more, preferably 25 to 60% by mass, and more preferably 30 to 70% by mass. When the F content is not less than the lower limit of the above range, the Abbe number of the cured product is sufficiently high. When the F content is not more than the upper limit of the above range, the compatibility with other components is good. The compound (B) includes a compound (B1) in which a group other than the (meth) acryloyloxy group is a linear fluoroalkyl group or a fluoroalkylene group, and a group other than the (meth) acryloyloxy group having a branched structure, −O. -Or, a compound (B2) having -NH- or the like is included.

As the compound (B), fluoro (meth) acrylate is preferable from the viewpoint of compatibility with other components.
Examples of the fluoro (meth) acrylate include the following compounds. All of the following compounds have an F content of 20% by mass or more.
Compound (B1):
CH ₂ = CHC (O) OCH (CF ₃ ) ₂ ,
CH ₂ = C (CH ₃ ) C (O) OCH (CF ₃ ) ₂ ,
CH ₂ = CHC (O) O (CH ₂ ) ₂ (CF ₂ ) ₁₀ F,
CH ₂ = CHC (O) O (CH ₂ ) ₂ (CF ₂ ) ₈ F,
CH ₂ = CHC (O) O (CH ₂ ) ₂ (CF ₂ ) ₆ F,
CH ₂ = C (CH ₃ ) C (O) O (CH ₂ ) ₂ (CF ₂ ) ₁₀ F,
CH ₂ = C (CH ₃ ) C (O) O (CH ₂ ) ₂ (CF ₂ ) ₈ F,
CH ₂ = C (CH ₃ ) C (O) O (CH ₂ ) ₂ (CF ₂ ) ₆ F,
CH ₂ = CHC (O) OCH ₂ (CF ₂ ) ₆ F,
CH ₂ = C (CH ₃ ) C (O) OCH ₂ (CF ₂ ) ₆ F,
CH ₂ = CHC (O) OCH ₂ (CF ₂ ) ₇ F,
CH ₂ = C (CH ₃ ) C (O) OCH ₂ (CF ₂ ) ₇ F,
CH ₂ = CHC (O) OCH ₂ CF ₂ CF ₂ H,
CH ₂ = CHC (O) OCH ₂ (CF ₂ CF ₂ ) ₂ H,
CH ₂ = CHC (O) OCH ₂ (CF ₂ CF ₂ ) ₄ H,
CH ₂ = CHC (O) OCH ₂ (CF ₂ ) ₄ CH ₂ OC (O) CH = CH ₂ ,
CH ₂ = C (CH ₃ ) C (O) OCH ₂ (CF ₂ ) ₄ CH ₂ OC (O) C (CH ₃ ) = CH ₂ etc.
Compound (B2):
CH ₂ = CHC (O) OCH ₂ CH (OH) CH ₂ CF ₂ CF ₂ CF (CF ₃ ) ₂ ,
CH ₂ = C (CH ₃ ) C (O) OCH ₂ CH (OH) CH ₂ CF ₂ CF ₂ CF (CF ₃ ) ₂ ,
CH ₂ = C (CH ₃ ) C (O) OCH ₂ CF ₂ CF ₂ H,
CH ₂ = C (CH ₃ ) C (O) OCH ₂ (CF ₂ CF ₂ ) ₂ H,
CH ₂ = C (CH ₃ ) C (O) OCH ₂ (CF ₂ CF ₂ ) ₄ H,
CH ₂ = CHC (O) OCH ₂ CF ₂ OCF ₂ CF ₂ OCF ₃ ,
CH ₂ = CHC (O) OCH ₂ CF ₂ O (CF ₂ CF ₂ O) ₃ CF ₃ ,
CH ₂ = C (CH ₃ ) C (O) OCH ₂ CF ₂ OCF ₂ CF ₂ OCF ₃ ,
CH ₂ = C (CH ₃ ) C (O) OCH ₂ CF ₂ O (CF ₂ CF ₂ O) ₃ CF ₃ ,
CH ₂ = CHC (O) OCH ₂ CF (CF ₃ ) OCF ₂ CF (CF ₃ ) O (CF ₂ ) ₃ F,
CH ₂ = CHC (O) OCH ₂ CF (CF ₃ ) O (CF ₂ CF (CF ₃ ) O) ₂ (CF ₂ ) ₃ F,
CH ₂ = C (CH ₃ ) C (O) OCH ₂ CF (CF ₃ ) OCF ₂ CF (CF ₃ ) O (CF ₂ ) ₃ F,
CH ₂ = C (CH ₃ ) C (O) OCH ₂ CF (CF ₃ ) O (CF ₂ CF (CF ₃ ) O) ₂ (CF ₂ ) ₃ F,
CH ₂ = CFC (O) OCH ₂ CH (OH) CH ₂ (CF ₂ ) ₆ CF (CF ₃ ) ₂ ,
CH ₂ = CFC (O) OCH ₂ CH (CH ₂ OH) CH ₂ (CF ₂ ) ₆ CF (CF ₃ ) ₂ ,
CH ₂ = CFC (O) OCH ₂ CH (OH) CH ₂ (CF ₂ ) ₁₀ F,
CH ₂ = CFC (O) OCH ₂ CH (CH ₂ OH) CH ₂ (CF ₂ ) ₁₀ F,
CH ₂ = CHC (O) OCH ₂ CF ₂ (OCF ₂ CF ₂ ) _p OCF ₂ CH ₂ OC (O) CH = CH ₂ (where p is an integer of 1 to 20),
CH ₂ = C (CH ₃ ) C (O) OCH ₂ CF ₂ (OCF ₂ CF ₂ ) _p OCF ₂ CH ₂ OC (O) C (CH ₃ ) = CH ₂ (where p is an integer from 1 to 20) be.),
CH ₂ = CHC (O) O (CH ₂ ) ₂ NHC (O) OCH ₂ (CF ₂ ) ₃ OCHFCF ₂ O (CH ₂ ) ₂ OCF ₂ CFHO (CF ₂ ) ₃ CH ₂ OC (O) NH (CH ₂ ) ) ₂ OC (O) CH = CH ₂ etc.
As the compound (B), one kind may be used alone, or two or more kinds may be used in combination.

(Compound (C))
The compound (C) has one or more (meth) acryloyl groups (excluding the same as the surface-modified metal oxide particles (A) and the compound (B)).
As the compound (C), a compound in which an organic group having 1 to 30 carbon atoms is bonded to a (meth) acryloyl group via an oxygen atom is preferable. The organic group preferably has 4 to 20 carbon atoms, more preferably 4 to 12 carbon atoms. Examples of the organic group include a linear alkyl group, a branched alkyl group, a cycloalkyl group, an allyl group, a bridging hydrocarbon group, a group having a repeating structure of an oxyalkylene chain, an aromatic group, a heterocyclic group and the like. In these groups, a part of the carbon atom may be substituted with a hetero atom such as a nitrogen atom or an oxygen atom or a silicon atom, and a part of the hydrogen atom is substituted with a functional group such as a hydroxyl group or an amino group. It may also have an unsaturated bond or a free carboxy group. As the organic group, a linear alkyl group, a branched alkyl group, a cycloalkyl group and a bridging hydrocarbon group are preferable.

The compound (C) includes a compound (C1) having one (meth) acryloyloxy group, a compound (C2) having two or more (meth) acryloyloxy groups, and a compound (C) alone. It may be used, or two or more kinds may be used in combination.
As the compound (C1), an acrylic acid ester or a methacrylic acid ester is preferable. Examples of the compound (C1) include known compounds.
Examples of the compound (C2) include (meth) acrylate of diol (glycol, etc.), (meth) acrylate of triol (glycerol, trimethylol, etc.), (meth) acrylate of tetraol (pentaerythritol, etc.), and urethane (meth) acrylate. , Epoxy (meth) acrylate is preferred. Examples of the compound (C2) include known compounds.

(Polymer Initiator (D))
The polymerization initiator (D) is appropriately selected depending on the curing method (photo-curing or thermosetting) and the like.
Examples of the polymerization initiator (D) include a photopolymerization initiator or a thermal polymerization initiator. As the polymerization initiator (D), a photopolymerization initiator is preferable from the viewpoint of ease of producing a cured product.
Examples of the photopolymerization initiator include a photoradical polymerization initiator that generates radicals by absorbing light. As the photopolymerization initiator, a photoradical polymerization initiator is preferable from the viewpoint of ease of producing a cured product.

Examples of the photoradical polymerization initiator include an alkylphenone-based photopolymerization initiator, an acylphosphine oxide-based photopolymerization initiator, a titanosen-based photopolymerization initiator, an oxime ester-based photopolymerization initiator, and an oxyphenyl acetate-based photopolymerization initiator. Benzoin-based photopolymerization initiator, benzophenone-based photopolymerization initiator, thioxanthone-based photopolymerization initiator, benzyl- (o-ethoxycarbonyl) -α-monooxime, glyoxyester, 3-ketocoumarin, 2-ethylanthraquinone, camphorquinone. , Tetramethylthium sulfide, azobisisobutyronitrile, benzoyl peroxide, dialkyl peroxide, tert-butyl peroxypivalate and the like. From the viewpoint of sensitivity and compatibility, an alkylphenone-based photopolymerization initiator, an acylphosphine oxide-based photopolymerization initiator, a benzoin-based photopolymerization initiator or a benzophenone-based photopolymerization initiator is preferable. As the photopolymerization initiator, one type may be used alone, or two or more types may be used in combination.

Examples of the thermal polymerization initiator include 2,2'-azobisisobutyronitrile, benzoyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, di-tert-butyl peroxide, dicumyl peroxide and the like. From the viewpoint of decomposition temperature, 2,2'-azobisisobutyronitrile and benzoyl peroxide are preferable. As the thermal polymerization initiator, one type may be used alone, or two or more types may be used in combination.

The curable composition of the present invention may contain a compound (C), an additive, a solvent and the like, if necessary.
Examples of the above additives include surfactants, antioxidants (heat-stabilizing agents), thixotropic agents, defoaming agents, light-resistant stabilizers, anti-gelling agents, photosensitizers, resins, resin oligomers, carbon compounds, and metals. Examples thereof include fine particles, metal oxide particles (excluding those same as the surface-modified metal oxide particles (A)), silane coupling agents, and other organic compounds.

As the solvent, any solvent can be used as long as it can dissolve the compound (B), (C) and the polymerization initiator (D), and any one of an ester structure, a ketone structure, a hydroxyl group and an ether structure can be used. A solvent having the above is preferable. The content of the solvent in the curable composition may be appropriately adjusted depending on the desired viscosity, coatability, target film thickness and the like. When a solvent is used, it is preferable to remove the solvent before curing the curable composition.

(Ratio of each component of curable composition)
The ratio of the surface-modified metal oxide particles (A) is 100 mass in total of the surface-modified metal oxide particles (A) and all the compounds having (meth) acryloyl groups (excluding the particles (A)). Of the percentage, it is 1 to 90% by mass, preferably 3 to 85% by mass, and more preferably 5 to 80% by mass. When the ratio is equal to or higher than the lower limit of the above range, the Abbe number of the cured product is high. When the ratio is not more than the upper limit of the above range, the compatibility with other components is good, the surface-modified metal oxide particles (A) are easily dispersed uniformly in the curable composition, and the cured product becomes transparent. Excellent.

The ratio of the compound (B) is 10 out of a total of 100% by mass of the surface-modified metal oxide particles (A) and all the compounds having (meth) acryloyl groups (excluding the particles (A)). It is ~ 99% by mass, preferably 15 to 97% by mass, more preferably 20 to 95% by mass. When the ratio is at least the lower limit of the above range, the compatibility with other components is good and the transparency of the cured product is excellent. When the ratio is not more than the upper limit of the above range, the Abbe number of the cured product is sufficiently high.
The ratio of the compound (B1) is 40 out of a total of 100% by mass of the surface-modified metal oxide particles (A) and the compound having all (meth) acryloyl groups (excluding the particles (A)). It is preferably from 99% by mass, more preferably 60 to 94% by mass, still more preferably 80 to 89% by mass. When the ratio is at least the lower limit of the above range, the compatibility with other components is good and the transparency of the cured product is excellent. When the ratio is not more than the upper limit of the above range, the Abbe number of the cured product is sufficiently high.
The ratio of the compound (B2) is 10 out of 100% by mass of the total of the surface-modified metal oxide particles (A) and the compound having all (meth) acryloyl groups (however, excluding the particles (A)). It is preferably ~ 99% by mass, more preferably 15 to 97% by mass, still more preferably 20 to 95% by mass. When the ratio is at least the lower limit of the above range, the compatibility with other components is good and the transparency of the cured product is excellent. When the ratio is not more than the upper limit of the above range, the Abbe number of the cured product is sufficiently high.
When the curable composition of the present invention contains the compound (B1), the proportion of the surface-modified metal oxide particles (A) is preferably 1 to 60% by mass, more preferably 6 to 40% by mass, and 11 to 11 to 20% by mass is more preferable.

When the curable composition of the present invention contains the compound (C), the proportion of the compound (C) is such that the surface-modified metal oxide particles (A) and the compound having all (meth) acryloyl groups (provided that the particles (provided as described above). Of the total 100% by mass excluding A)), it is 1 to 50% by mass, preferably 3 to 45% by mass, and more preferably 5 to 40% by mass. When the ratio is at least the lower limit of the above range, the compatibility of each component is enhanced and the transparency of the cured product is excellent. When the ratio is not more than the upper limit of the above range, the Abbe number of the cured product is high.
When the curable composition of the present invention contains the compound (C), the proportion of the surface-modified metal oxide particles (A) is 1 to 89% by mass, preferably 3 to 82% by mass, and 5 to 75% by mass. Is more preferable.
When the curable composition of the present invention contains the compound (C), the proportion of the compound (B) is 10 to 98% by mass, preferably 15 to 94% by mass, and more preferably 20 to 90% by mass. The ratio of the compound (B1) is preferably 40 to 98% by mass, more preferably 60 to 91% by mass, still more preferably 80 to 84% by mass. The ratio of the compound (B2) is preferably 10 to 98% by mass, more preferably 15 to 94% by mass, still more preferably 20 to 90% by mass.

The amount of the polymerization initiator (D) added is 100 parts by mass in total of the surface-modified metal oxide particles (A) and all the compounds having (meth) acryloyl groups (excluding the particles (A)). On the other hand, it is 0.01 to 10 parts by mass, preferably 0.1 to 7 parts by mass, and more preferably 0.3 to 5 parts by mass. When the addition amount is at least the lower limit of the above range, a cured product can be easily formed. When the addition amount is not more than the upper limit of the above range, the mixture can be uniformly mixed, so that the amount of the polymerization initiator (D) remaining in the cured product is reduced, and the deterioration of the physical properties of the cured product is suppressed.

The total amount of other components added, such as additives, may be as long as it does not impair the effects of the present invention, and is a compound having surface-modified metal oxide particles (A) and all (meth) acryloyl groups (provided that the compound has all (meth) acryloyl groups. 5 parts by mass or less is preferable, and 3 parts by mass or less is more preferable with respect to 100 parts by mass in total with the particles (A).
<Curing product>
The cured product of the present invention is a cured product of the curable composition of the present invention. The cured product of the present invention may be formed on the surface of the base material to form a laminate having a layer made of the cured product and a layer made of the base material.
The Abbe number obtained from the above formula (I) of the cured product is preferably 58 or more, more preferably 60 or more. If it is at least the lower limit of the above range, chromatic aberration is unlikely to occur. The higher the Abbe number, the better, and the upper limit is not particularly limited, but it is about 70 considering that it is an organic substance.

The transmittance of the cured product with a wavelength of 600 nm is preferably 60% or more, more preferably 65% or more. When the light transmittance is at least the above lower limit value, the transparency of the cured product is further excellent.
The transmittance of the cured product with a wavelength of 600 nm is 25 ° C. using light with a wavelength of 600 nm by the method described in JIS K 7361: 1997 (ISO 13468-1: 1996) for a cured product having a thickness of 10 to 200 μm. Be measured.

(Manufacturing method of cured product)
As a method for producing a cured product of the present invention, the curable composition is cured in a state where a mold having an inverted pattern of a fine pattern on the surface and the curable composition are in contact with each other to have the fine pattern on the surface. A method of forming a cured product (imprint method); a method of injecting a curable composition into a cavity of a mold and curing the curable composition to form a cured product (casting molding method) and the like can be mentioned. ..
Examples of the curing method include photo-curing or thermosetting, which may be appropriately selected depending on the polymerization initiator (D). As a curing method, photo-curing is preferable from the viewpoint of ease of producing a cured product.

Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited thereto.
Examples 5 to 8, 11, 17, 18, 25 to 28, and 33 are examples, and Examples 1 to 4, 9, 10 , 13 to 16, 19 to 24, 29 to 32, and 34 to 38 are compared. It is an example, and Example 12 is a reference example .

(Median diameter)
The median diameters of the surface-modified metal oxide particles and the metal oxide particles before surface modification were determined using a particle size distribution measuring instrument (manufactured by Otsuka Electronics Co., Ltd., FPAR1000) by a dynamic light scattering method.

(The amount of heat weight loss)
The surface-modified metal oxide particles were heated from 18 ° C. to 550 ° C. at a rate of 25 ° C./min under a nitrogen atmosphere using a thermogravimetric measuring device (TAGA-Q500, manufactured by TA Instruments), and the thermogravimetric analysis was performed. The amount of decrease was measured.

(Infrared spectrum)
Infrared spectroscopic spectra of surface-modified metal oxide particles were measured using a Fourier transform infrared spectrophotometer (NICOLET iN10 + iZ10, manufactured by Thermo Fisher Scientific).

(Solid ¹⁹ F-NMR)
For the surface-modified metal oxide particles, a solid ¹⁹ F-NMR spectrum was measured using a nuclear magnetic resonance spectrum measuring device (AVANCE-III HD manufactured by Bruker Biospin).

(Viscosity of curable composition)
The viscosity of the curable composition was determined by measuring the dynamic viscoelasticity at a shear rate of 10s ^-1 at 25 ° C. using a dynamic viscoelasticity measuring device (Physica MCR501, manufactured by Antonio Par).

(Refractive index of dispersion and curable composition)
The refractive index of the dispersion and the curable composition was measured using an Abbe refractometer (multi-wavelength Abbe refractometer DR-M2 manufactured by Atago) at a temperature of 25 ° C. and a wavelength of 589 nm.

(Abbe number of dispersion and curable composition)
The Abbe number of the dispersion and the curable composition is determined from the following formula (I) by measuring the refractive indexes of the wavelengths: 589 nm, 486 nm, and 656 nm at a temperature of 25 ° C. using an Abbe refractometer (same as above). Calculated.
ν _D = (n _D -1) / (n _F -n _C ) (I)

(Refractive index of cured product)
The curable composition was applied to the surface of the silicon wafer and irradiated with ultraviolet rays from a high-pressure mercury lamp at an exposure amount of 3000 mJ / cm ² , to form a film-like cured product. The refractive index of the cured product with respect to light having a wavelength of 473 nm, 594 nm and 658 nm was measured using a refractive index measuring device (prism coupler manufactured by Metricon, USA: 2010 / M), and light having a wavelength of 589 nm was measured using the Metricon Fit attached to the device. The index of refraction was calculated.

(Abbe number of cured product)
The refractive index at each wavelength was calculated using the Metaricon Fit attached to the refractive index measuring device, and the Abbe number was calculated from the above equation (I).

(Hardened product for evaluation)
A curable composition was applied to the surface of the glass substrate, and ultraviolet rays were irradiated from a high-pressure mercury lamp at an exposure amount of 3000 mJ / cm ² to form a film-like cured product. The cured product was peeled off from the glass substrate to obtain a cured product for evaluation.

(Transmittance of dispersion and cured product)
The transmittance of the dispersion liquid and the cured product for evaluation with respect to light having a wavelength of 600 nm was measured using an ultraviolet / visible / near-infrared spectrophotometer (Solid Spec-3700, manufactured by Shimadzu Corporation).

(Metal oxide particles)
Aqueous dispersion of metal oxide particles (Z): zirconia sol (manufactured by Sakai Chemical Industry Co., Ltd., SZR-W, ZrO ₂ concentration: 30% by mass, median diameter: 4.4 nm (dynamic light scattering method), pH: 4 .3, Refractive index of zirconia particles with respect to light having a wavelength of 589 nm: 2.075 (externalized from the refractive index of 30% by mass aqueous dispersion).
Aqueous dispersion of metal oxide particles (T): rutile type titania sol (manufactured by Sakai Chemical Industry Co., Ltd., SRD-W, TiO ₂ concentration: 15% by mass, median diameter: 4.2 nm (dynamic light scattering method), pH: 2.2 Refractive index of titania particles with respect to light having a wavelength of 589 nm: 2.323 (externalized from the refractive index of 15 mass% aqueous dispersion).

(Compound (A10))
Compound (A10-1): Trifluoropropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-7103).
Compound (A10-2): Trimethoxy (1H, 1H, 2H, 2H-heptadecafluorodecyl) silane (manufactured by Tokyo Chemical Industry Co., Ltd.).

(Compound (A20))
Compound (A20-1): 3-methacryloyloxypropyltrimethoxysilane (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.).
Compound (A20-2): 8-methacryloyloxyoctyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-5803).

(Fluorine-containing organic solvent)
HCFC-225: Dichloropentafluoropropane (manufactured by Asahi Glass Co., Ltd., Asahi Kulin (registered trademark) AK-225, F content: 47% by mass).

(Compound (B))
Compound (B-1): CH ₂ = C (CH ₃ ) C (O) O (CH ₂ ) ₂ (CF ₂ ) ₆ F (manufactured by Asahi Glass Co., Ltd., F content: 57% by mass).
Compound (B-2): CH ₂ = CHC (O) OCH ₂ CF ₂ (OCF ₂ CF ₂ ) ₂ OCF ₂ CH ₂ OC (O) CH = CH ₂ (manufactured by Shin Nakamura Chemical Industry Co., Ltd., NK ester DA-F4EO) , F content: 44% by mass).

(Polymer Initiator (D))
Polymerization Initiator (D-1): Photoradical Polymerization Initiator (BASF Japan, Inc., trade name, Irgacure 184).

(Example 1)
33 g of the aqueous dispersion of the metal oxide particles (Z) was placed in a 500 mL beaker and 167 g of ethanol was added. While stirring with a magnetic stirrer, 12.3 g of compound (A10-1) and 3.6 g of compound (A10-2) were added, and stirring was continued at room temperature for 7 days. An azeotropic substance of ethanol and water was removed using an evaporator, and the mixture was concentrated to a liquid volume of 50 mL to obtain a concentrated liquid. 250 mL of water was placed in a 500 mL beaker, and the concentrate was added over 5 minutes while stirring with a magnetic stirrer to make the mixture cloudy. Stirring was continued for 1 day at room temperature, the precipitate was collected with a filter, and the precipitate was washed with 500 mL of water to obtain 25 g of a white solid containing water.

The obtained white solid was placed in a 500 mL eggplant flask, 300 g of stirrer chip and methyl isobutyl ketone (MIBK) was added, a Dean Stark dehydrator was attached, and the mixture was heated to 130 ° C. in an oil bath with stirring. As the water was removed, the transparency of the liquid in the flask increased, and when water did not come out after 3 hours, 1 g of triethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the transparency was high after 2 minutes. It became a dispersion liquid. After cooling, the volatile matter is distilled off from the dispersion liquid using an evaporator, dried, and further dried in a vacuum dryer at 70 ° C. for 15 hours to obtain the powder of the surface-modified oxide fine particles (AZ'-1). 15 g was obtained.

The ratio of the surface-modified organic component was determined from the amount of thermogravimetric reduction of the surface-modified metal oxide particles (AZ'-1). Solid ¹⁹ F-NMR spectrum of surface-modified metal oxide particles (AZ'-1) with ₃ peaks of -CF derived from compound (A10-1) and ₁₇ groups of -C ₈ F derived from compound (A10-2). From the peak intensity ratio, the ratio of the two types of first surface modifying groups was determined. The composition of the surface-modified metal oxide particles (AZ'-1) is shown in Table 1.

(Example 2)
The synthesis was carried out in the same manner as in Example 1 except that the charge amount of the compound (A10-1) was changed to 6.9 g and the charge amount of the compound (A10-2) was changed to 17.8 g, and the surface-modified metal oxide was prepared. 17 g of particles (AZ'-2) were obtained.
The ratio of the two types of first surface modifying groups was determined by the same method as in Example 1. The composition of the surface-modified metal oxide particles (AZ'-2) is shown in Table 1.

(Example 3)
The synthesis was carried out in the same manner as in Example 1 except that the charge amount of the compound (A10-1) was changed to 20.7 g and the charge amount of the compound (A10-2) was changed to 5.4 g, and the surface-modified metal oxide was prepared. 22 g of particles (AZ'-3) were obtained.
The ratio of the two types of first surface modifying groups was determined by the same method as in Example 1. The composition of the surface-modified metal oxide particles (AZ'-3) is shown in Table 1.

(Example 4)
The synthesis was carried out in the same manner as in Example 1 except that the charge amount of the compound (A10-1) was changed to 7.8 g and the charge amount of the compound (A10-2) was changed to 16.1 g, and the surface-modified metal oxide was prepared. 20 g of particles (AZ'-4) were obtained.
The ratio of the two types of first surface modifying groups was determined by the same method as in Example 1. The composition of the surface-modified metal oxide particles (AZ'-4) is shown in Table 1.

(Example 5)
The same method as in Example 1 except that the charged amount of the compound (A10-1) was changed to 12.3 g without adding the compound (A10-2), and 1.6 g of the compound (A20-1) was further added. To obtain 18 g of surface-modified metal oxide particles (AZ-5).
The ratio of the surface-modified organic component was determined from the amount of thermogravimetric reduction of the surface-modified metal oxide particles (AZ-5). Peaks from -CF ₃ groups near 1260 cm ^-1 derived from compound (A10-1) and 1750 cm ^-1 derived from compound (A20-1) in the infrared spectroscopic spectrum of surface-modified metal oxide particles (AZ-5). From the intensity ratio of the peak derived from C = O in the vicinity, the ratio of the first surface modifying group and the ratio of the second surface modifying group were determined. The composition of the surface-modified metal oxide particles (AZ-5) is shown in Table 1.

(Example 6)
The same method as in Example 1 except that the charge amount of the compound (A10-1) was changed to 12.5 g without adding the compound (A10-2), and 2.0 g of the compound (A20-2) was further added. To obtain 18 g of surface-modified metal oxide particles (AZ-6).
The ratio of the first surface modifying group and the ratio of the second surface modifying group were determined by the same method as in Example 5. The composition of the surface-modified metal oxide particles (AZ-6) is shown in Table 1.

(Example 7)
Example 1 except that the charge amount of the compound (A10-1) was changed to 11.3 g, the charge amount of the compound (A10-2) was changed to 4.8 g, and 0.7 g of the compound (A20-1) was further added. The synthesis was carried out in the same manner as in the above to obtain 18 g of surface-modified metal oxide particles (AZ-7).
The ratio of the two types of the first surface modifying group and the ratio of the second surface modifying group were determined by the same method as in Example 5. The composition of the surface-modified metal oxide particles (AZ-7) is shown in Table 1.

(Example 8)
Example 1 except that the charged amount of the compound (A10-1) was changed to 7.7 g, the charged amount of the compound (A10-2) was changed to 14.1 g, and 0.6 g of the compound (A20-1) was further added. The synthesis was carried out in the same manner as in the above to obtain 19 g of surface-modified metal oxide particles (AZ-8).
The ratio of the two types of the first surface modifying group and the ratio of the second surface modifying group were determined by the same method as in Example 5. The composition of the surface-modified metal oxide particles (AZ-8) is shown in Table 2.

(Example 9)
The surface was synthesized by the same method as in Example 1 except that the aqueous dispersion of the metal oxide particles (Z) was changed to 66 g of the aqueous dispersion of the metal oxide particles (T) and the amount of ethanol was changed to 234 g. 17 g of modified metal oxide particles (AT'-1) were obtained.
The ratio of the two types of first surface modifying groups was determined by the same method as in Example 1. The composition of the surface-modified metal oxide particles (AT'-1) is shown in Table 2.

(Example 10)
The surface was synthesized by the same method as in Example 2 except that the aqueous dispersion of the metal oxide particles (Z) was changed to 66 g of the aqueous dispersion of the metal oxide particles (T) and the amount of ethanol was changed to 234 g. 18 g of modified metal oxide particles (AT'-2) were obtained.
The ratio of the two types of first surface modifying groups was determined by the same method as in Example 1. The composition of the surface-modified metal oxide particles (AT'-2) is shown in Table 2.

(Example 11)
The surface was synthesized by the same method as in Example 7 except that the aqueous dispersion of the metal oxide particles (Z) was changed to 66 g of the aqueous dispersion of the metal oxide particles (T) and the amount of ethanol was changed to 234 g. 20 g of modified metal oxide particles (AT-3) were obtained.
The ratio of the two types of the first surface modifying group and the ratio of the second surface modifying group were determined by the same method as in Example 5. The composition of the surface-modified metal oxide particles (AT-3) is shown in Table 2.

(Example 12)
The surface was synthesized by the same method as in Example 8 except that the aqueous dispersion of the metal oxide particles (Z) was changed to 66 g of the aqueous dispersion of the metal oxide particles (T) and the amount of ethanol was changed to 234 g. 20 g of modified metal oxide particles (AT-4) were obtained.
The ratio of the second surface modifying group was determined by the same method as in Example 5. The composition of the surface-modified metal oxide particles (AT-4) is shown in Table 2.

(Example 13)
The synthesis was carried out in the same manner as in Example 1 except that 15.6 g of the compound (A20-1) was added without adding the compound (A10-1) and the compound (A10-2), and the surface-modified metal oxide was added. 19 g of particles (AZ'-13) were obtained.
The ratio of the surface-modified organic component was determined from the amount of thermogravimetric reduction of the surface-modified metal oxide particles (AZ'-13). The composition of the surface-modified metal oxide particles (AZ'-13) is shown in Table 2.

(Example 14)
Without adding the compound (A10-1) and the compound (A10-2), the aqueous dispersion of the metal oxide particles (Z) was changed to 66 g of the aqueous dispersion of the metal oxide particles (T), and the compound (A20-) was changed. The synthesis was carried out in the same manner as in Example 1 except that 15.1 g of 1) was added and the amount of ethanol was changed to 234 g to obtain 17 g of surface-modified metal oxide particles (AT'-5).
The ratio of the surface-modified organic component was determined from the amount of thermogravimetric reduction of the surface-modified metal oxide particles (AT'-5). The composition of the surface-modified metal oxide particles (AT'-5) is shown in Table 2.

(Example 15)
The synthesis was carried out in the same manner as in Example 1 except that ethanol was changed to 2-propanol, and 16 g of surface-modified metal oxide particles (AZ'-9) was obtained.
The ratio of the two types of first surface modifying groups was determined by the same method as in Example 1. The composition of the surface-modified metal oxide particles (AZ'-9) is shown in Table 3 .

(Example 16)
Synthesis was carried out in the same manner as in Example 1 except that the amount of compound (A10-1) charged was 7.5 g, the amount of compound (A10-2) charged was 16.6 g, and ethanol was changed to 2-propanol. This was carried out to obtain 16 g of surface-modified metal oxide particles (AZ'-10).
The ratio of the two types of first surface modifying groups was determined by the same method as in Example 1. The composition of the surface-modified metal oxide particles (AZ'-10) is shown in Table 3 .

(Example 17)
33 g of the aqueous dispersion of the metal oxide particles (Z) was placed in a 500 mL beaker, and 167 g of 2-propanol and 84 g of compound (B-1) were added. While stirring with a magnetic stirrer, add 12.0 g of compound (A10-1), 3.8 g of compound (A10-2) and 1.5 g of compound (A20-1), and stir at room temperature for 3 days. Continued. The azeotropic product of 2-propanol and water was removed using an evaporator and concentrated until the liquid volume reached 100 mL to obtain a concentrated liquid. 500 mL of hexane was placed in a 1 L beaker, and the concentrate was added over 10 minutes while stirring with a magnetic stirrer to make the mixture cloudy. Stirring was continued for 1 day at room temperature, the precipitate was collected with a filter and washed with 500 mL of hexane to give 28 g of a white solid containing hexane and water.

The obtained white solid was placed in a 500 mL eggplant flask, 300 g of stirrer chip and methyl isobutyl ketone (MIBK) was added, a Dean Stark dehydrator was attached, and the mixture was heated to 130 ° C. in an oil bath with stirring. As the water was removed, the transparency of the liquid in the flask increased, and when water did not come out after 2 hours, 1 g of triethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the transparency was high after 1 minute. It became a dispersion liquid. After cooling, the volatile matter was distilled off from the dispersion liquid using an evaporator, dried, and further dried in a vacuum dryer at 70 ° C. for 18 hours to obtain 16 g of powder of surface-modified oxide fine particles (AZ-11). Got

(Example 18)
The synthesis was carried out in the same manner as in Example 17 except that the charge amount of the compound (A10-1) was changed to 7.5 g and the charge amount of the compound (A10-2) was changed to 16.6 g, and the surface-modified metal oxide was prepared. 18 g of particles (AZ-12) were obtained.
The ratio of the two types of the first surface modifying group and the ratio of the second surface modifying group were determined by the same method as in Example 1. The composition of the surface-modified metal oxide particles (AZ-12) is shown in Table 3.

(Example 19 )
0.05 g of surface-modified metal oxide particles (AZ'-1) and 0.95 g of HCFC-225 are mixed, and an ultrasonic homogenizer (manufactured by Nissei Tokyo Office, US-) is used to uniformly disperse the particles. By irradiating ultrasonic waves at an oscillation frequency of 20 kHz for 2 hours using 300T), a uniform dispersion with haze was obtained. When the surface-modified metal oxide particles are agglomerated, the agglomerates can be crushed by performing the above-mentioned ultrasonic irradiation. Even if the dispersion was left at room temperature for one month, no precipitate was deposited, and the other side of the dispersion was at a level where it could be visually recognized. The evaluation results of the dispersion liquid are shown in Table 4 .

(Example 20 )
0.05 g of the surface-modified metal oxide particles (AZ'-1), 0.95 g of the compound (B-1) and 0.01 g of the polymerization initiator (D-1) were mixed under the same conditions as in Example 19 . By ultrasonic irradiation, a uniform curable composition with haze was obtained. The evaluation results of the curable composition are shown in Table 4 .

(Examples 21, 23, 24, 29, 31 )
A transparent and uniform dispersion was obtained by performing ultrasonic irradiation under the same conditions as in Example 19 except that the type of the surface-modified metal oxide particles (A) was changed. The evaluation results of the dispersion liquid are shown in Table 4, Table 5 , and Table 6 .

(Examples 22, 25, 26, 30, 32 )
A transparent and uniform curable composition was obtained by performing ultrasonic irradiation under the same conditions as in Example 19 except that the type of the surface-modified metal oxide particles (A) was changed. The evaluation results of the curable composition are shown in Tables 4, 5 and 6 .

(Example 27 )
0.05 g of the surface-modified metal oxide particles (AZ-7), 0.95 g of the compound (B-2) and 0.01 g of the polymerization initiator (D-1) were mixed, and the cells were subjected to the same conditions as in Example 19 . By irradiating with ultrasonic waves, a transparent and uniform curable composition was obtained. The evaluation results of the curable composition are shown in Table 5 .

(Examples 28 and 33 )
A transparent and uniform curable composition was obtained by performing ultrasonic irradiation under the same conditions as in Example 19 except that the type of the surface-modified metal oxide particles (A) was changed. The evaluation results of the curable composition are shown in Tables 5 and 6.

(Example 34 )
0.05 g of surface-modified metal oxide particles (AZ'-3), 0.05 g of surface-modified metal oxide particles (AT'-2) and 0.90 g of HCFC-225 were mixed, and the same conditions as in Example 19 were used. A transparent and uniform dispersion was obtained by irradiating with ultrasonic waves .

(Examples 35 to 36 )
In order to disperse 10% by mass of the surface-modified metal oxide particles (AZ'-9) to 90% by mass of MIBK, ultrasonic irradiation was performed under the same conditions as in Example 19 , and a transparent and uniform dispersion liquid was obtained. rice field.
Attempts to disperse 1% by weight of surface-modified metal oxide particles (AZ'-9) into 99% by weight (Example 35 ) of HCFC-225 or 99% by weight (Example 36 ) of compound (B-1). However, none of them could be dispersed, and ultrasonic irradiation was performed under the same conditions as in Example 19 except that the irradiation time was changed to 15 hours, but the surface-modified metal oxide particles (AZ'-9) remained precipitated. It was .

(Examples 37-38)
In order to disperse 10% by mass of the surface-modified metal oxide particles (AT'-5) to 90% by mass of MIBK, ultrasonic irradiation was performed under the same conditions as in Example 19 , and a transparent and uniform dispersion liquid was obtained. rice field.
An attempt was made to disperse 1% by mass of surface-modified metal oxide particles (AT'-5) in 99% by mass (Example 37) of HCFC-225 or 99% by mass (Example 38) of compound (B-1). However, none of them could be dispersed, and ultrasonic irradiation was performed under the same conditions as in Example 19 except that the irradiation time was changed to 15 hours, but the surface-modified metal oxide particles (AT'-5) remained precipitated. there were.

Examples 19 to 35 contain surface-modified metal oxide particles having a specific fluoroalkyl group-containing surface modifying group, and therefore have a high Abbe number and excellent transparency. However, in Examples 19 to 24 and 29 to 32 , the surface-modified metal oxide particles do not have a specific (meth) acryloyl group-containing surface-modifying group, and thus are inferior in curability.
In Examples 37 to 38, since the surface-modified metal oxide particles do not have a fluoroalkyl group-containing surface modifying group, the compatibility with the fluorine-containing compound is poor, the particles are not uniformly dispersed in the fluorine-containing compound, and the transparency is poor. ..

The surface-modified metal oxide particles, dispersion liquid, and curable composition of the present invention are used for manufacturing optical members (lenses, prisms, antireflection films, optical waveguides, LED encapsulants, etc.), recording media, semiconductor devices, and the like. It is useful as a material.

The entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2015-254093 filed on December 25, 2015 are cited here and incorporated as disclosure of the specification of the present invention. It is a thing.

Claims (14)

It is represented by the first surface modifying group having a group represented by the following formula (A1) and the following formula (A2) on the surface of the metal oxide particles having a refractive index of 1.9 or more with respect to light having a wavelength of 589 nm. Surface-modified metal oxide particles having a second surface-modifying group having a group.
C _n F _m H _{2n + 1-m-} SiR ¹ _a (-*) _3-a (A1)
(* Is a bond of Si, R ¹ is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, n is an integer of 1 to 20, and m is an integer of 3 or more (2n + 1) or less. , A is an integer of 0 to 2, and when a is 2, the two ^R1s may be the same or different.)
CH ₂ = CR ³ C (O) -X- (CH ₂ ) _b -SiR ⁴ _c (-*) _3-c (A2)
(* Is a bond of Si, R ³ is a hydrogen atom or a methyl group, R ⁴ is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, and X is -O- or -NH-. , B is an integer of 2 to 10, c is an integer of 0 to 2, and when c is 2, the two ^R4s may be the same or different.) The ratio of the metal oxide particles to 100% by mass of the surface-modified metal oxide particles is 20 to 84% by mass, and the surface-modified organic component (total of the first surface-modifying group and the second surface-modifying group). The surface-modified metal oxide particles according to claim 1, wherein the (containing) ratio is 16 to 80% by mass. Claim 1 or claim 1, wherein the ratio of the first surface modifying group is 15 to 55% by mass and the ratio of the second surface modifying group is 1 to 25% by mass in 100% by mass of the surface-modified metal oxide particles. 2. The surface-modified metal oxide particles according to 2. A surface-modified metal that surface-treats the surface of metal oxide particles having a refractive index of 1.9 or more with respect to light having a wavelength of 589 nm by the compound represented by the following formula (A10) and the compound represented by the following formula (A20). Method for producing oxide particles.
C _n F _m H _{2n + 1-m-} SiR ¹ _a (OR ² ) _3-a (A10)
(R ¹ , a, m and n are the same as the definitions in the formula (A1) of claim 1, respectively. R ² is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and a is 0. Or the three or ^two R2s in the case of 1 may be the same or different.)
CH ₂ = CR ³ C (O) -X- (CH ₂ ) _b -SiR ⁴ _c (OR ⁵ ) _3-c (A20)
(R ³ , R ⁴ , b and c are the same as the definitions in the formula (A2) of claim 1, respectively. R ⁵ is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and c is. The three or two ^R5s in the case of 0 or 1 may be the same or different. Of the total 100% by mass of the compound represented by the formula (A10) and the compound represented by the formula (A20), the compound represented by the formula (A10) is 39 to 98% by mass, and the formula is described above. The method for producing surface-modified metal oxide particles according to claim 4, wherein the compound represented by (A20) is 2 to 61% by mass. The fourth or fifth aspect of the present invention, wherein the total amount of the compound represented by the formula (A10) and the compound represented by the formula (A20) is 65 to 1360 parts by mass with respect to 100 parts by mass of the metal oxide particles. A method for producing surface-modified metal oxide particles. The surface-modified metal oxide particles according to any one of claims 1 to 3 and
It contains a fluorine-containing compound having a fluorine atom content of 20% by mass or more and being liquid at 25 ° C.
Of the total 100% by mass of the surface-modified metal oxide particles and the fluorine-containing compound, the surface-modified metal oxide particles are 1 to 90% by mass, and the fluorine-containing compound is 10 to 99% by mass. Dispersion solution. The dispersion liquid according to claim 7, wherein the Abbe index obtained from the following formula (I) is 58 or more, and the transmittance of light having a wavelength of 600 nm is 40% or more.
ν _D = (n _D -1) / (n _F -n _C ) (I)
(Ν _D is the Abbe number, n _D is the index of refraction for light with a wavelength of 589 nm, n _F is the index of refraction for light with a wavelength of 486 nm, and n _C is the index of refraction for light with a wavelength of 656 nm. be.) The surface-modified metal oxide particles (A) according to any one of claims 1 to 3 and the surface-modified metal oxide particles (A).
Compound (B) having a fluorine atom content of 20% by mass or more and having one or more (meth) acryloyl groups (excluding the same particles as the particles (A)).
Including the polymerization initiator (D)
Of the total 100% by mass of the particles (A) and all compounds having (meth) acryloyl groups (excluding the particles (A)), the particles (A) are 1 to 90% by mass. Yes, the compound (B) is 10 to 99% by mass,
The polymerization initiator (D) is 0.01 with respect to a total of 100 parts by mass of the particles (A) and all the compounds having (meth) acryloyl groups (excluding the particles (A)). A curable composition of up to 10 parts by mass. (Meta) A compound (C) having one or more acryloyl groups (excluding the same as the particles (A) or the compound (B)) is further contained.
Of the total 100% by mass of all compounds having (meth) acryloyl groups (including the particles (A)), the particles (A) are 1 to 89% by mass, and the compound (B) is. The curable composition according to claim 9, wherein the content is 10 to 98% by mass, and the compound (C) is 1 to 50% by mass. The curable composition according to claim 9 or 10, wherein the compound (B) is a fluoro (meth) acrylate. The compound (C) is a compound (C1) having one (meth) acryloyloxy group, or a compound (C2) having two or more (meth) acryloyloxy groups (however, the compounds (C1) and (C2) are The curable composition according to claim 10, which is the same as the particles (A) or the compound (B). (Meta) A compound (C) having one or more acryloyl groups (excluding the same as the particles (A) or the compound (B)) is further contained.
Of the total 100% by mass of all the compounds having (meth) acryloyl groups (including the particles (A)), the particles (A) are 1 to 89% by mass, and the compound (B) is. It is 10 to 98% by mass, and the compound (C) is 1 to 50% by mass.
Compound (B) is a fluoro (meth) acrylate, and the compound (B) is
The compound (C) is a compound (C1) having one (meth) acryloyloxy group, or a compound (C2) having two or more (meth) acryloyloxy groups (however, the compounds (C1) and (C2) are The curable composition according to claim 9, which is the same as the particles (A) or the compound (B). A cured product obtained by curing the curable composition according to any one of claims 9 to 13.